Sciencemadness Discussion Board

Room temperature Swern

Paddywhacker - 5-6-2010 at 22:24

Everyone is familiar with the famous Swern oxidation. It is a favourite in textbooks and in industrial and academic labs. But it isn't used much by amateurs because, for one, it uses oxalyl chloride which is difficult to obtain and a bitch to handle, and secondly it requires dry-ice/acetone temperatures.

Apparently, acetic anhydride and a number of other compounds can substitute as activators of the DMSO, and because they are not as active as oxalyl chloride they can be used at room temp.

Here is a chapter out of a book that discusses this subject

Edit:- Heh, the PDF is too big, even when compressed.

Never mind, the book is "Oxidation of Alcohols to Aldehydes and Ketones" by Gabriel Tojo & Marcos Fernandez, 2006, Springer Science.
Library of Congress Control Number: 2005927383
ISBN-10: 0-387-23607-4
ISBN-13: 978-0387-23607-0


[Edited on 6-6-2010 by Paddywhacker]

not_important - 5-6-2010 at 23:49

You could use ifile.it to stash it.

Paddywhacker - 6-6-2010 at 01:38

Thanks NI, here is the url.

DJF90 - 6-6-2010 at 12:18

Moffatt type oxidations are well known and I've got that book also. The only downside to such reactions are that dimethyl sulfide is formed as a biproduct. Each set of conditions is advantageous for various substates, and although you point out the lack of need for oxalyl chloride, a large number of them use inaccessible reagents such as TFAA, SO3-Py, DCC/PyTFA, NCS/Me2S, Me2S/Cl2, P2O5 etc. The Kornblum oxidation is also a useful synthetic method that makes use of DMSO as an oxidant.

JohnWW - 6-6-2010 at 16:38

Ifile.it has gone down, having been out for at least a few hours now. However, I will see if I can find that complete book as a PDF or DJVU file, and upload it to my rapidshare.com account.

Paddywhacker - 6-6-2010 at 17:58

Quote: Originally posted by DJF90  
Moffatt type oxidations are well known and I've got that book also. The only downside to such reactions are that dimethyl sulfide is formed as a biproduct. Each set of conditions is advantageous for various substates, and although you point out the lack of need for oxalyl chloride, a large number of them use inaccessible reagents such as TFAA, SO3-Py, DCC/PyTFA, NCS/Me2S, Me2S/Cl2, P2O5 etc. The Kornblum oxidation is also a useful synthetic method that makes use of DMSO as an oxidant.


I can live with dimethyl sulphide, but if you look at the end of the book - the whole book - you'll see DMS being oxidized with a halogen to give the same activated reagent that is produced by activating DMSO ... so maybe it can be reused catalytically until it is all consumed by side-reactions.

None of these Moffatt-types is side-product free, but the reagents are cheap and available.

JWW, can't remember where I downloaded the book, but I see it as a file in a big multi-gig torrent of chem books. It's probably in the reference section too.

DJF90 - 7-6-2010 at 08:17

I've read the WHOLE book. What you are talking about is the *actual* Corey Kim oxidation - not the modification that uses NCS. It's disfavoured in practice because the actual reaction between DMS and chlorine is a PITA, and hence the use of NCS. Catalytic use of dimethyl sulfide may work, but I'd have expected them to have thought and tried it at the time of discovering the reaction, and I haven't heard of such things.

Sandmeyer - 8-6-2010 at 17:49

SWiS already mentioned Albright-Goldman oxidation once (UTFSE!), well, their seminal papers are following:
____
Dimethyl Sulfoxide-Acid Anhydride Mixtures. New Reagents for Oxidation of Alcohols

J. Donald Albright, Leon Goldman
J. Am. Chem. Soc., 1965, 87 (18), pp 4214–4216
DOI: 10.1021/ja01096a055
_____
Dimethyl sulfoxide-acid anhydride mixtures for the oxidation of alcohols

J. Donald. Albright, Leon. Goldman
J. Am. Chem. Soc., 1967, 89 (10), pp 2416–2423
DOI: 10.1021/ja00986a031
_____
Indole Alkaloids. III. Oxidation of Secondary Alcohols to Ketones
J. Donald Albright, Leon Goldman
J. Org. Chem., 1965, 30 (4), pp 1107–1110
DOI: 10.1021/jo01015a038
_____

In a related, interesting application, Upjohn chemists used Albright-Goldman reagent to oxidise aldehydes to -COOH as well as amides (via aldehyde bisulfite adducts):

The oxidation of aldehyde bisulfite adducts to carboxylic acids and their derivatives with dimethylsulfoxide and acetic anhydride

Tet. Lett. Vol. 27, 1986, pp. 3995-3998